Process of manufacturing condensation products from formaldehyde, tannin, and aromatic monohydroxyl compounds.



on-the-Saale, Kingdom of Prussia, and Ger- UNITED STATES FATEN T ()FFICE.

HERMANN HILDEBRANDT, OF HALLE-ON-THE-SAALE, GERMANY.

PROCESS OF MANUFACTURING CONDENSATION PRODUCTS FROM FORMALDEHYDE, TANNIN, AND AROMATIC MONOHYDROXYL COMPOUNDS.

N0. 878,811. I Specification of Letters Patent. Patented J an. 7, 19 )8.

' Application filed February 21. 1907. Serial No. 358.579- (Specimens) To all whom itmay concern: I droXyl-grou as obtained before my inven- Be it known that I, HERMANN HILDE- tion, have 'or instance been manufactured BRANDT, a doctor of medicine, and a subject l both with formaldehyde alone as well as with of the German Emperor, and a resident of I formaldehyde and a phenolic body, such as 22 Magdeburger-strasse, in the city of Halleresorcin, tannin and the like, and from cotoin,

, the active principle of the coto-bark, which man Empire, have mventeda certain new constitutes the 4-methyl-cther of the 2-4-6- and useful Process for Manufacturing (onl trioxybenzophenon, being a derivative of the densation Products from Formaldehyde, phloroglucin and possessing the formula Tannin, and Aromatic Monohydroxyl (done H C H (OH) OCH pounds, of which the following is a specihcation. By condensation with formaldehyde alone This invention has reference to condensacotoinformsn1ethylen-cotoin (ll. ,((),,lI,,O tion products of formaldehyde with tannin or while condensat ion with cotoin and a phenolic tannic axid of any source whatever with that bodyproduces substitution products of the class of henolic bodies, which contain only cotoin, such ,as methylen cotoin tannin. one free ydroxyl-group, but no other free or Other condensation products with formaldesubstituted hydroxyl-groups, such as ordihyde heretofore known, are those obtained nary henol, thymol, airvacrol, ci'eosol, from formaldehyde and tannin with guaiacol, Xylenol: alphaand beta-napthol, salicylic l or with wood creosote, or with eugenol or acid. By condensation with formaldehyde, pyrogallol and the ether derivatives of these the said class of bodies, by replacing the odies. The condensation product with oxygen of the formaldehyde, form comguaiacol is described in French Patent pounds containing inono-oXy-benzyl or the 280851 and patent of addition thereto, the 1 8 a ph HA DCH C(Jlllcreosote condensation product is described pounds of this kind have been found to be in British Patent 5650/1899. valuable remedies and they have proved to l From all the previously known condensabe especially valuable in diseases of the inl tion products referred to, my invention is testinal' tract. They possess the decided distinguished by producing bodies all of astringent properties of the ordinary tannin which contain the monoxyd enzyl radical, or tannic acid, which properties are still insometimes also called the metlmn-phenolecreased by the combination with the phenolic radical C,,ll .()l-I.Cll, and no additional free body, and they are free from any injurious or substituted hydroxyl. These bodies ar irritating action 11 on the intestinal system. also distinguished by the novel therapeutic Owing to the insolilbilit-y in acid of the moeffect which they produce upon the human noxy-benzyl-compounds mentioned above, system, that is to say their absence of injuthey will not clog the intestinal tract and will rious irritating action. not overtax the stomach and theyprodnce a The preparation of the new tannin or more decided and more reliable antiseptic actannic acid compounds is preferably effected tion in the intestinal system, in View of the by mixing the alcoholic solution of the parphenol-derivatives contained in their respccticular phenolic body with the aqueous solutivemolecules, than those condensation prodtion of tannin, using molecular quantities of nets heretofore obtained by thecondensation each substance, thus for instance 15 grains of formaldehyde with phenolic bodies, conthymol, or 9.4 grams phenol and 32.2 grams taining more than one free or substituted hytannic acid and then adding to this mixture droX l-group, the astringent properties of two or three times the amount of the calcuwhici compounds were very defective and lated quantity of a 40-per. cent. solution of were accompanied by very marked, irritatl formaldehyde. While the mass is being ing roperties. Formaldehydecondensation kept constantly stirred, the mixture is then pro ucts of this kind, that is to say with phepoured into twenty times the amount of nolic bodies, containing either two free or two i concentrated hydrochloric acid of say 38% substituted hydroXyl-groups or one free hy- I [Cl which would correspond to the amount droXyl-group and another substituted hyof tannin or tannic acid employed. The

amount of hydrochloric acid should be at least ten times the volume of the combined alcoholic and aqueous solutions of the phenolic body, formaldehyde and tannin or tannic acid. After allowing to stand for some time, dilute with water, in order to facilitate the subsequent removal of the acid. The precipitate, obtained by the treatment with the mineral acid is then washed with water, in order to remove the bulk of the acid, though for ordinary uses it is not necessary to wash out every trace of hydrochloric acid. The washing may either be done on a filter or by decantation in a tall vessel, where the precipitate is allowed to deposit and the liquid is poured off. Then the precipitate is finally dried at ordinary temperature, which may be facilitated in the ordinary manner by first sucking elf from the precipitate ,the moisture, yet adhering to it. The condensation product is obtained by the pouring of the mixture into the acid which precipitates the said product. 'If desired, the precipitate may also be washed at once after precipitation; it is however sometimes desirable to' allow to stand for a short time, so as to allow 1 i itate to collect.

It is of course i what source the tannin or tannic at "5? a place of ordinary tannic acid tan nic acid containing drugs may l: such as extracts of nut-galls, of canai f cute h,

of oak bark.

The process is applicable to phenolic bodies of any kind, of the class referred to and free from oxy-all yl-groups and instead of the derivatives of the benzolic series, the deriva tives of the naphthalene, such as alphanaphthol, and beta-naphthol may be used. The process may also be applied to the ester combinations of the phenolic bodies men tioned, such as acetyl-thymol, benzoylthymol, acteyl-salicylic acid. Thus the following compounds may be obtained: tanninphenol-methan Cll,((l,,lI,O)--(G i-I O be ing a loose, whitish powder which is insoluble in alcohol and. soluble in alkalies; it does not melt at 240 degreescentigrade. T anninthymol-methan (lll ttl li O) m i. is a faintly colored, odorless powder which is readily soluble in alcohol, from which solution it can not be precipitated by water. It is soluble in alkalies and melts with decomosition at about 235 degrees centigrade. The condensation by which these products are formed and by which one molecule of water is set free, is effected by the removal of one atom of hydrogen from each of the two substances which combine with the Cll.,group, the said hydrogen being removed from the i i l l l i in the case of the above mentioned thymol compound.

What 1 claim and desire to secure by Letters Patent of the United States is 2- 1. The process of manufacturing cond according to the following ensation products from tannin by means of formaldehyde, which process consists in mixing a solution of any substance of the aromatic series containing one free unsubstituted hydroxyl-group and free from substituted oxy-groups, wlth a solution of a tannin in substantially molecular proportions, addi formaldehyde to the mixture produce largely in excess of the theoretical quantity,

pouring the mixture thus obtained in a great excess of hydrochloric acid, to produce condensation, separating the precipitate obtained and drying said precipitate.

2. The process of manufacturing condensation products from tannin by means of formaldehyde, which process consists in ing a soiution of any aromatic compound taming monoxy-benzyl with a solution ii '.i substantially molecular quanti formaldehyde largely in excess e/cal quantity, pouring the mixobtainer. in a great excess of hydro to produce condensation and n, separating the precipitate obtained and drying said precipitate.

of manufacturing condensation products from tannin by means of formaldehyde, which process consists in mixing an alcoholic solution of thymol with a watery solution of a tannin, in substantially molecular proportions, adding 40% formaldehyde largely in excess of the theoretical quantity, pouring the mixture thus obtained in a great excess of concentrated hydrochloric acid to produce condensation and precipitation, separating the precipitate from the liquid, and then washing the precipitate and drying said precipitate.

4. The herein described condensation product of thymol with formaldehyde and tannin, the said product being )recipit...

3. The process lnsoluble in water, and soluble in alkali, and soluble in alcohol, and melting with decomposition at about 235 degrees centigrade.

Signed at Leipzig, Germany of February, 1907.

IIERMANN HILDEBRANDT. \Vitnesses:

RuDoLrn FRICKE, SOUTHARD P. WARNER.

this 5th day 

